CN111489016B - Universal prediction method and system suitable for reactivity of pyrolysis coke of solid fuel - Google Patents
Universal prediction method and system suitable for reactivity of pyrolysis coke of solid fuel Download PDFInfo
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Abstract
The invention discloses a general prediction method and a general prediction system for coke reactivity of solid fuel pyrolysis, which relate to the field of solid fuel thermochemical conversion and mainly comprise the steps of obtaining characteristic parameters and reaction working conditions of a solid fuel sample, dividing the components into different microstructures according to contributions of different components of the solid fuel sample to coke pores, obtaining characteristic parameters and structural factors of the coke pores according to the characteristic parameters of the solid fuel sample, obtaining initial reactivity of the coke in a non-catalytic state according to the characteristic parameters and the reaction working conditions of the coke, and obtaining catalytic factors according to the content of internal catalytic elements; and obtaining the initial reactivity of the pyrolysis coke of the solid fuel sample according to the initial reactivity of the coke in the non-catalytic state and the catalytic factor, and predicting the full conversion process of the coke reactivity by combining a random pore model. The invention utilizes the gas-solid collision theory of reaction dynamics and the fractal characteristics of the coke pore structure to realize the whole-process prediction of the coke reaction rate.
Description
Technical Field
The invention relates to the field of solid fuel thermochemical conversion, in particular to a general calculation method suitable for predicting the reactivity of pyrolysis coke of solid fuel.
Background
Solid fuels include coal, biomass, petroleum coke, oil shale, and trash, among others. In many high-value utilization modes of solid fuels, a thermochemical conversion technology can convert the solid fuels into high-grade combustible gases and byproducts with high added values such as tar, coke and the like.
Thermochemical conversion technology consists essentially of two processes: pyrolysis of solid fuel and gasification of coke, the solid composed of carbon and ash remaining after the volatilization of the solid fuel is coke, and the content of coke is only 10-30% of pyrolysis products, but the gasification time is 80-90% of the total process, which determines the overall residence time. Therefore, coke is taken as an intermediate, a correlation mechanism of pyrolysis and gasification processes is grasped theoretically, and a general method for calculating the reactivity of the pyrolysis coke is obtained, so that the residence time of fuel in the gasification furnace can be determined, and reference can be provided for the design of the gasification furnace.
The gasification furnace is used as core equipment of a thermochemical conversion process, and the design method depends on the characteristics and the operation conditions of solid fuel in the furnace, however, a set of prediction methods for wide adaptability to the fuel and the operation conditions still is lacking at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a general prediction method and a general prediction system for the reactivity of the coke by pyrolysis of solid fuel, which are used for realizing the whole process prediction of the reaction rate of the coke by utilizing the gas-solid collision theory of reaction dynamics and the fractal characteristic of the pore structure of the coke.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a universal prediction method suitable for solid fuel pyrolysis coke reactivity, comprising the steps of:
step 1: obtaining solid fuel sample characteristic parameters and reaction conditions, wherein the solid fuel sample characteristic parameters comprise industrial analysis data, element analysis data, initial porosity, internal catalytic element content and coke particle size, and the reaction conditions comprise reaction gas pressure, reaction temperature and concentration of reaction gas components and corresponding components;
step 2: dividing the components into different microstructures according to the contributions of different components of the solid fuel sample to the coke pores, obtaining characteristic parameters and structural factors of the coke pores according to characteristic parameters of the solid fuel sample, obtaining initial reactivity of the coke in a non-catalytic state according to the characteristic parameters and reaction conditions of the coke, and obtaining catalytic factors according to the content of internal catalytic elements;
step 3: and obtaining the initial reactivity of the pyrolysis coke of the solid fuel sample according to the initial reactivity of the coke in the non-catalytic state and the catalytic factor, and predicting the full conversion process of the coke reactivity by combining a random pore model.
A universal prediction system for the reactivity of pyrolysis coke of a solid fuel, comprising:
an input unit: the method is used for acquiring solid fuel sample characteristic parameters and reaction conditions, wherein the solid fuel sample characteristic parameters comprise industrial analysis data, element analysis data, initial porosity, internal catalytic element content and coke particle size, and the reaction conditions comprise reaction gas pressure, reaction temperature, reaction gas components and concentrations of corresponding components;
a calculation unit: the method is used for dividing the components into different microstructures according to the contributions of different components of the solid fuel sample to the coke pores, obtaining characteristic parameters and structural factors of the coke pores according to characteristic parameters of the solid fuel sample, obtaining initial reactivity of the coke in a non-catalytic state according to the characteristic parameters and reaction conditions of the coke pores, and obtaining catalytic factors according to the content of internal catalytic elements;
prediction unit: the method is used for obtaining the initial reactivity of the pyrolysis coke of the solid fuel sample according to the initial reactivity of the coke in a non-catalytic state and the catalytic factor, and predicting the full conversion process of the coke reactivity by combining a random pore model;
and a display unit: which is used for showing the relation of coke reactivity with conversion rate according to the prediction result of the prediction unit.
Compared with the prior art, the invention has the beneficial effects that: the invention utilizes the gas-solid collision theory of reaction dynamics and the fractal characteristics of the coke pore structure to realize the whole-process prediction of the coke reaction rate. According to the method, the coke reaction rate can be directly predicted through the input of the sample characteristic parameters and the reaction working conditions, so that the experimental analysis and test flow of the coke is reduced, and the calculation is convenient. The invention can provide theoretical guidance for the design of the industrial gasification furnace, so that the size design of the gasification furnace can be dependent, and the design process is more efficient and convenient. The invention can provide theoretical reference for the residence time of the sample in the industrial gasification furnace, and theoretically grasp the burnout time of the fuel; meanwhile, the pyrolysis coke reactivity of different fuels can be compared, so that the performances of different fuels can be compared.
Drawings
FIG. 1 is a flow chart of a general prediction method applicable to the pyrolysis coke reactivity of solid fuel according to an embodiment of the present invention;
FIG. 2 is a graph of coke reactivity versus conversion for an example of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and detailed description.
Examples:
referring to fig. 1, a general prediction method suitable for the reactivity of pyrolysis coke of solid fuel comprises the following steps:
step 1: : the method comprises the steps of obtaining solid fuel sample characteristic parameters and reaction conditions, wherein the solid fuel sample characteristic parameters comprise industrial analysis data, element analysis data, initial porosity, internal catalytic element content and coke particle size, and the reaction conditions comprise reaction gas pressure, reaction temperature, reaction gas components and concentrations of corresponding components.
Step 2: according to the contribution of different components of the solid fuel sample to the coke pore space, the components are divided into different microstructures, according to the characteristic parameters of the solid fuel sample, the characteristic parameters and the structural factors of the coke pore space are obtained, according to the characteristic parameters and the reaction conditions of the coke pore space, the initial reactivity of the coke in a non-catalytic state is obtained, and according to the content of the internal catalytic elements, the catalytic factors are obtained. According to the method, from the characteristic of the sample, the characteristic parameters of the coke pores can be theoretically solved, a traditional adopted BET experiment detection method of the coke sample is replaced, the calculation is more convenient, and the result is more reliable.
Step 3: and obtaining the initial reactivity of the pyrolysis coke of the solid fuel sample according to the initial reactivity of the coke in the non-catalytic state and the catalytic factor, and predicting the full conversion process of the coke reactivity by combining a random pore model. The random pore model considers pore distribution, and in a plurality of structural function models, the random pore model is a model capable of predicting the position where the maximum reaction rate occurs, and meanwhile, the random pore model parameters obtained by calculation in the step can replace the random pore model parameters obtained by the traditional experimental curve fitting method, so that theoretical solution of the random pore model parameters is realized.
In step 1, the industrial analysis data includes ash content of the solid fuel, fixed carbon content of the solid fuel, and volatile content of the solid fuel, and the elemental analysis data includes carbon element, hydrogen element, nitrogen element, sulfur element, and oxygen element content. The elemental analysis data includes carbon, hydrogen, nitrogen, sulfur, and oxygen content, the internal catalytic elements include positive and negative catalytic elements, and the positive catalytic element content includes: the negative catalytic element content is silicon element content and aluminum element content.
In step 2, if the solid fuel contains two main components, the solid fuel is divided into a component I and a component II according to the porosity of the coke after pyrolysis of each component, and the two components undergo a pyrolysis process to generate a certain amount of microstructure monomers, correspondingly, the microstructure monomers generated by pyrolysis of the component I are named as microstructure I, and the microstructure monomers generated by pyrolysis of the component II are named as microstructure II. Assuming the coke is spherical in shape, the pores in the coke are cylindrical and the microstructure is spherical.
The structural factors of microstructure I and microstructure II are respectively ψ I And psi is II ：
Wherein y is I And y II Fixed carbon content, l, of component I and component II, respectively b And d b The length and diameter of the pores in microstructure I, respectively, l s And d s Respectively the length and diameter of the pores in microstructure II, epsilon 0 Is the initial porosity of the sample.
Microstructure I andthe number of the microstructures II is N respectively I And N II ：
Wherein d is char Particle size of coke, epsilon b And epsilon s Porosity of microstructure I and microstructure II, respectively.
The porosities of microstructure I and microstructure II are ε, respectively b And epsilon s ：
Wherein V is char For the volume of coke, V 0 FA is the ash content of the solid fuel, η is the fraction of component I, which is the volume of the solid fuel feedstock.
The ratio eta of the component I:
where FC is the fixed carbon content of the solid fuel.
Wherein ρ is t The true density of the non-porous graphite is equal to 2250kg/M3, A is the Avofacillo constant, M vI And M vII The relative molecular masses of the volatile monomers in component I and component II are indicated, respectively.
Relative molecular mass M of volatile monomers v ：
Wherein C, H, O, N, S represents the contents of carbon element, hydrogen element, oxygen element, nitrogen element and sulfur element, respectively, in the elemental analysis.
The catalytic factor gamma:
wherein eta c,i Active site area ratio, eta, of inorganic element i with forward catalysis in coke c,K The active site area ratio of potassium element in coke, eta j Active site area ratio, beta, of inorganic element j with negative catalysis in coke c,K Is the catalysis multiplying power, T, of the potassium element in a complete catalysis state 0 For the determination of the catalytic index, alpha i,0 At a temperature T 0 Catalytic index, alpha, of element i measured at the time j,0 At a temperature T 0 The catalytic index of the element j is measured, and T is the gasification reaction temperature;
active site area ratio eta of catalytic element i c,i ：
Wherein w is i For the mass fraction of catalytic element i, r i Radius of van der Waals force action for catalytic element i, r C Is the Van der Waals force acting radius of the carbon element, M C Is the relative atomic mass of carbon element, M i Is the relative atomic mass of catalytic element i.
Catalytic multiplying power beta of potassium element in complete catalytic state c,K ：
Wherein k is c,K And E is c,K Respectively refers to the exponential front factor and the activation energy, k of the gasification/combustion reaction of the carbon matrix under the complete catalysis state of the potassium element n And E is n The pre-exponential factor and the activation energy of the gasification/combustion reaction of the carbon matrix in the non-catalytic state, respectively.
Coke reactivity in non-catalytic state:
wherein R is N0 For initial stage coke reactivity, P j And M j The pressure and the relative molecular mass of the reaction gas j are respectively, and the reaction gas can be carbon dioxide, water vapor, oxygen or mixed gas with known components and concentration ratio, M C Is the relative atomic mass of carbon, R is a universal gas constant, E n Is based on the activation energy of simple collision theory in chemical reaction kinetics.
In step 3, coke reactivity R:
R＝R 0 ·f(x)＝R N0 ·γ·f(x)
where x is the coke conversion, γ is the catalytic factor, R is the coke reactivity at conversion x, f (x) is the structural function,
where ψ is a structural factor related to the coke pore structure,
ψ＝ηN I ψ I +(1-η)N II ψ II 。
in this embodiment, a typical woody biomass sample pine wood in a solid fuel is taken as an example, and it is generally considered that biomass mainly comprises three components of cellulose, hemicellulose and lignin, and coke is mainly produced by pyrolysis of lignin, so that cellulose and hemicellulose are divided into component I, the corresponding pyrolysis coke is composed of a certain number of microstructures I, lignin is divided into component II, and the corresponding pyrolysis coke is composed of a certain number of microstructures II.
The elemental analysis and industrial analysis data (mass percentages of the elements, the following are the same) of the pine samples to be input are as follows:
C＝48.43％；
H＝6.20％；
N＝0.01％；
S＝0.02％；
O＝44.87％；
FC＝9.83％；
FV＝89.70％；
FA＝0.47％.
the average particle diameter d of coke produced by pyrolysis of pine wood particles with the particle diameter of less than 60 microns char 45.85 micrometers, initial porosity ε of pine 0 ＝0.3。
Elemental analysis and industrial analysis data for lignin are as follows:
C＝61.86％；
H＝5.81％；
N＝1.00％；
S＝0；
O＝27.35％；
FC＝27.83％；
FV＝72.17％；
FA＝0.
elemental analysis and industrial analysis data for cellulose are as follows:
C＝43.38％；
H＝6.50％；
N＝1.00％；
S＝0；
O＝49.12％；
FC＝1.46％；
FV＝98.54％；
FA＝0.
setting reaction conditions: the reaction gas adopts CO with the purity of 99.999 percent 2 The reaction temperature was t=725 ℃, and the reaction pressure was P j ＝1atm。
The pore characteristic parameters obtained by the calculation in the step two are as follows:
Ψ I ＝0.043
Ψ II ＝1.63
N I ＝1555.02
N II ＝4416.00
ε b ＝0.42
ε s ＝0.28
l b ＝373.01nm
l s ＝232.02nm
d b ＝1.046nm
d s ＝0.353nm
the calculated cellulose fraction in the sample was:
η＝0.667
the calculated relative molecular mass of the cellulose, lignin and volatile monomers in the sample is as follows:
M vI ＝810.64g/mol
M vII ＝31.12g/mol
M v ＝109.55g/mol
the inorganic element content with catalysis effect (i.e. the internal catalytic element content) of the pine sample to be input is as follows:
potassium element: w (w) K ＝276.53mg/Kg
Sodium element: w (w) Na ＝357.69mg/Kg
Calcium element: w (w) Ca ＝306.91mg/Kg
Magnesium element: w (w) Mg ＝103.39mg/Kg
Elemental iron: w (w) Fe ＝696.86mg/Kg
Elemental silicon: w (w) Si ＝5564.48mg/Kg
Aluminum element: w (w) Al ＝3062.01mg/Kg
From the above input parameters, the calculated catalytic factors are:
γ＝20.58
the coke reactivity model in the non-catalytic state is as follows
R 0 ＝0.00047min -1
The structural factor is
Ψ＝0.572
The obtained change relation graph of the coke reactivity along with the conversion rate is shown in figure 2, and the method utilizes the gas-solid collision theory of reaction dynamics and the fractal characteristic of the coke pore structure to realize the whole-process prediction of the coke reaction rate.
A universal prediction system for the reactivity of pyrolysis coke of a solid fuel, comprising:
an input unit: the method is used for obtaining solid fuel sample characteristic parameters and reaction conditions, wherein the solid fuel sample characteristic parameters comprise industrial analysis data, element analysis data, initial porosity, internal catalytic element content and coke particle size, and the reaction conditions comprise reaction gas pressure, reaction temperature, reaction gas components and concentrations of corresponding components.
A calculation unit: the method is used for dividing the components into different microstructures according to the contributions of different components of the solid fuel sample to the coke pores, obtaining characteristic parameters and structural factors of the coke pores according to characteristic parameters of the solid fuel sample, obtaining initial reactivity of the coke in a non-catalytic state according to the characteristic parameters and reaction conditions of the coke, and obtaining catalytic factors according to the content of internal catalytic elements.
Prediction unit: the method is used for obtaining the initial reactivity of the pyrolysis coke of the solid fuel sample according to the initial reactivity of the coke in a non-catalytic state and the catalytic factor, and predicting the full conversion process of the coke reactivity by combining a random pore model.
And a display unit: which is used for showing the relation of coke reactivity with conversion rate according to the prediction result of the prediction unit.
Further, in the input unit, the industrial analysis data includes ash content of the solid fuel, fixed carbon content of the solid fuel, and volatile content of the solid fuel, the elemental analysis data includes carbon element, hydrogen element, nitrogen element, sulfur element, and oxygen element content, the internal catalytic element includes positive catalytic element and negative catalytic element, and the positive catalytic element content includes: the negative catalytic element content is silicon element content and aluminum element content.
Further, in the computing unit, the processing unit,
the solid fuel comprises a component I and a component II, the two components undergo a pyrolysis process to produce two different microstructures I and II,
the structural factors of microstructure I and microstructure II are respectively ψ I And psi is II ：
Wherein y is I And y II Fixed carbon content, l, of component I and component II, respectively b And d b The length and diameter of the pores in microstructure I, respectively, l s And d s Respectively the length and diameter of the pores in microstructure II, epsilon 0 Initial porosity for the sample;
the number of microstructures I and II are N I And N II ：
Wherein d is char Particle size of coke, epsilon b And epsilon s Porosity of microstructure I and microstructure II, respectively;
the porosities of microstructure I and microstructure II are ε, respectively b And epsilon s ：
Wherein V is char For the volume of coke, V 0 FA is the ash content of the solid fuel, η is the fraction of component I;
the ratio eta of the component I:
wherein FC is the fixed carbon content of the solid fuel;
length l of the pores of microstructure I and microstructure II b ；l s And diameter d b ；d s ：
Wherein ρ is t The true density of the non-porous graphite is equal to 2250kg/M3, A is the Avofacillo constant, M vI And M vII Respectively representing the relative molecular masses of volatile monomers in the component I and the component II;
relative molecular mass M of volatile monomers v ：
Wherein C, H, O, N, S represents the contents of carbon element, hydrogen element, oxygen element, nitrogen element and sulfur element, respectively, in the elemental analysis.
Further, in the computing unit, the processing unit,
the catalytic factor gamma:
wherein eta c,i Active site area ratio, eta, of inorganic element i with forward catalysis in coke c,K The active site area ratio of potassium element in coke, eta j Active site area ratio, beta, of inorganic element j with negative catalysis in coke c,K Is the catalysis multiplying power, T, of the potassium element in a complete catalysis state 0 For the determination of the catalytic index, alpha i,0 At a temperature T 0 Catalytic index, alpha, of element i measured at the time j,0 At a temperature T 0 The catalytic index of the element j is measured, and T is the gasification reaction temperature;
active site area ratio eta of catalytic element i c,i ：
Wherein w is i For the mass fraction of catalytic element i, r i Radius of van der Waals force action for catalytic element i, r C Is the Van der Waals force acting radius of the carbon element, M C Is the relative atomic mass of carbon element, M i Is the relative atomic mass of catalytic element i;
catalytic multiplying power beta of potassium element in complete catalytic state c,K ：
Wherein k is c,K And E is c,K Respectively refers to the exponential front factor and the activation energy, k of the gasification/combustion reaction of the carbon matrix under the complete catalysis state of the potassium element n And E is n Respectively refers to the exponential front factor and the activation energy of gasification/combustion reaction of the carbon matrix in a non-catalytic state;
coke reactivity in non-catalytic state:
wherein R is N0 For initial stage coke reactivity, P j And M j The pressure and the relative molecular mass of the reaction gas j are respectively, and the reaction gas can be carbon dioxide, water vapor, oxygen or mixed gas with known components and concentration ratio, M C Is the relative atomic mass of carbon, R is a universal gas constant, E n Is based on the activation energy of simple collision theory in chemical reaction kinetics.
Further, in the prediction unit,
coke reactivity R:
R＝R 0 ·f(x)＝R N0 ·γ·f(x)
where x is the coke conversion, γ is the catalytic factor, R is the coke reactivity at conversion x, f (x) is the structural function,
where ψ is a structural factor related to the coke pore structure,
ψ＝ηN I ψ I +(1-η)N II ψ II 。
the system is used for the gas-solid collision theory of reaction dynamics and the fractal characteristic of the coke pore structure, so that the whole process prediction of the coke reaction rate is realized, and the change relation of the coke reactivity along with the conversion rate is displayed through images.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the essence of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A general prediction method for coke reactivity of solid fuel pyrolysis, comprising the steps of:
step 1: obtaining solid fuel sample characteristic parameters and reaction conditions, wherein the solid fuel sample characteristic parameters comprise industrial analysis data, element analysis data, initial porosity, internal catalytic element content and coke particle size, and the reaction conditions comprise reaction gas pressure, reaction temperature and concentration of reaction gas components and corresponding components;
step 2: dividing the components into different microstructures according to the contributions of different components of the solid fuel sample to the coke pores, obtaining characteristic parameters and structural factors of the coke pores according to characteristic parameters of the solid fuel sample, obtaining initial reactivity of the coke in a non-catalytic state according to the characteristic parameters and reaction conditions of the coke, and obtaining catalytic factors according to the content of internal catalytic elements;
step 3: obtaining initial reactivity of pyrolysis coke of a solid fuel sample according to initial reactivity of coke in a non-catalytic state and a catalytic factor, and predicting a full conversion process of the coke reactivity by combining a random pore model;
wherein the solid fuel is divided into a component I and a component II according to the porosity of the coke after pyrolysis of each component, the two components generate a certain amount of microstructure monomers through pyrolysis, the microstructure monomers generated by pyrolysis of the component I are microstructure I, the microstructure monomers generated by pyrolysis of the component II are microstructure II,
the structural factors of microstructure I and microstructure II are respectively ψ I And psi is II ：
Wherein y is I And y II Fixed carbon content, l, of component I and component II, respectively b And d b The length and diameter of the pores in microstructure I, respectively, l s And d s Respectively the length and diameter of the pores in microstructure II, epsilon 0 Initial porosity for the sample;
the number of microstructures I and II are N I And N II ：
Wherein d is char Particle size of coke, epsilon b And epsilon s Microstructures I and respectivelyPorosity of microstructure II;
the porosities of microstructure I and microstructure II are ε, respectively b And epsilon s ：
Wherein V is char For the volume of coke, V 0 FA is the ash content of the solid fuel, η is the fraction of component I;
the ratio eta of the component I:
wherein FC is the fixed carbon content of the solid fuel;
length of the pores of microstructure I b And diameter d b Length of the pores of microstructure II s And diameter d s ：
Wherein ρ is t True density of non-porous graphite, equal to 2250kg/m 3 A is an Avwherero constant, M vI And M vII Respectively representing the relative molecular masses of volatile monomers in the component I and the component II;
relative molecular mass M of volatile monomers v ：
Wherein C, H, O, N, S represents the contents of carbon element, hydrogen element, oxygen element, nitrogen element and sulfur element in the elemental analysis data, respectively;
the catalytic factor gamma:
wherein eta c,i Active site area ratio, eta, of inorganic element i with forward catalysis in coke c,K The active site area ratio of potassium element in coke, eta j Active site area ratio, N, of inorganic element j with negative catalysis in coke i Is a collection of inorganic elements i with positive catalysis, N j Beta is the set of inorganic elements j with negative catalysis c,K Is the catalysis multiplying power, T, of the potassium element in a complete catalysis state 0 For the determination of the catalytic index, alpha i,0 At a temperature T 0 Catalytic index, alpha, of element i measured at the time j,0 At a temperature T 0 The catalytic index of the element j is measured, and T is the gasification reaction temperature;
active site area ratio eta of catalytic element i c,i ：
Wherein w is i For the mass fraction of catalytic element i, r i Radius of van der Waals force action for catalytic element i, r C Is the Van der Waals force acting radius of the carbon element, M C Is the relative atomic mass of carbon element, M i Is the relative atomic mass of catalytic element i;
catalytic multiplying power beta of potassium element in complete catalytic state c,K ：
Wherein k is c,K And E is c,K Respectively refers to the exponential front factor and the activation energy, k of the gasification/combustion reaction of the carbon matrix under the complete catalysis state of the potassium element n And E is n Respectively refers to the exponential front factor and the activation energy of gasification/combustion reaction of the carbon matrix in a non-catalytic state;
initial reactivity of coke in non-catalytic state:
wherein P is g And M g The pressure and the relative molecular mass of the reaction gas g are respectively, and the reaction gas comprises any one of the following components: carbon dioxide, water vapor, oxygen or a mixture of known components and concentration ratios, M C R is a universal gas constant, and gamma is a catalytic factor;
coke reactivity R at conversion x x ：
R x ＝R 0 ·f(x)＝R N0 ·γ·f(x)
Wherein x is coke conversion, gamma is catalytic factor, R x R is the coke reactivity at conversion x 0 For the initial reactivity of the coke in the catalytic state, f (x) is a structural function,
where ψ is a structural factor related to the coke pore structure,
ψ＝ηN I ψ I +(1-η)N II ψ II 。
2. the universal predictive method for pyrolysis coke reactivity of solid fuels according to claim 1, wherein the industrial analytical data includes ash content of solid fuels, fixed carbon content of solid fuels and volatile content of solid fuels, the elemental analytical data includes carbon element, hydrogen element, nitrogen element, sulfur element and oxygen element content, the internal catalytic elements include positive catalytic elements and negative catalytic elements, the positive catalytic element content includes: the negative catalytic element content is silicon element content and aluminum element content.
3. A universal prediction system for the reactivity of pyrolysis coke of solid fuel, comprising:
an input unit: the method is used for acquiring solid fuel sample characteristic parameters and reaction conditions, wherein the solid fuel sample characteristic parameters comprise industrial analysis data, element analysis data, initial porosity, internal catalytic element content and coke particle size, and the reaction conditions comprise reaction gas pressure, reaction temperature, reaction gas components and concentrations of corresponding components;
a calculation unit: the method is used for dividing the components into different microstructures according to the contributions of different components of the solid fuel sample to the coke pores, obtaining characteristic parameters and structural factors of the coke pores according to characteristic parameters of the solid fuel sample, obtaining initial reactivity of the coke in a non-catalytic state according to the characteristic parameters and reaction conditions of the coke pores, and obtaining catalytic factors according to the content of internal catalytic elements;
prediction unit: the method is used for obtaining the initial reactivity of the pyrolysis coke of the solid fuel sample according to the initial reactivity of the coke in a non-catalytic state and the catalytic factor, and predicting the full conversion process of the coke reactivity by combining a random pore model;
and a display unit: the method is used for displaying the change relation of the coke reactivity with the conversion rate according to the prediction result of the prediction unit;
wherein in the computing unit, the solid fuel comprises a component I and a component II, the two components undergo a pyrolysis process to generate two different microstructures I and II, and the structural factors of the microstructures I and II are respectively psi I And psi is II ：
Wherein y is I And y II Fixed carbon content, l, of component I and component II, respectively b And d b The length and diameter of the pores in microstructure I, respectively, l s And d s Respectively the length and diameter of the pores in microstructure II, epsilon 0 Initial porosity for the sample;
the number of microstructures I and II are N I And N II ：
Wherein d is char Particle size of coke, epsilon b And epsilon s Porosity of microstructure I and microstructure II, respectively;
the porosities of microstructure I and microstructure II are ε, respectively b And epsilon s ：
Wherein V is char For the volume of coke, V 0 FA is the ash content of the solid fuel, η is the fraction of component I;
the ratio eta of the component I:
wherein FC is the fixed carbon content of the solid fuel;
length of the pores of microstructure I b And diameter d b Length of the pores of microstructure II s And diameter d s ：
Wherein ρ is t True density of non-porous graphite, equal to 2250kg/m 3 A is an Avwherero constant, M vI And M vII Respectively representing the relative molecular masses of volatile monomers in the component I and the component II;
relative molecular mass M of volatile monomers v ：
Wherein C, H, O, N, S represents the contents of carbon element, hydrogen element, oxygen element, nitrogen element and sulfur element in the elemental analysis data, respectively;
in the case of the calculation unit in question,
the catalytic factor gamma:
wherein eta c,i Active site area ratio, eta, of inorganic element i with forward catalysis in coke c,K The active site area ratio of potassium element in coke, eta j Active site area ratio, N, of inorganic element j with negative catalysis in coke i Is a collection of inorganic elements i with positive catalysis, N j Beta is the set of inorganic elements j with negative catalysis c,K Is the catalysis multiplying power, T, of the potassium element in a complete catalysis state 0 For the determination of the catalytic index, alpha i,0 At a temperature T 0 Catalytic index, alpha, of element i measured at the time j,0 At a temperature T 0 The catalytic index of the element j is measured, and T is the gasification reaction temperature;
active site area ratio eta of catalytic element i c,i ：
Wherein w is i For the mass fraction of catalytic element i, r i Radius of van der Waals force action for catalytic element i, r C Is the Van der Waals force acting radius of the carbon element, M C Is the relative atomic mass of carbon element, M i Is the relative atomic mass of catalytic element i;
catalytic multiplying power beta of potassium element in complete catalytic state c,K ：
Wherein k is c,K And E is c,K Respectively refers to the exponential front factor and the activation energy, k of the gasification/combustion reaction of the carbon matrix under the complete catalysis state of the potassium element n And E is n Respectively refers to the exponential front factor and the activation energy of gasification/combustion reaction of the carbon matrix in a non-catalytic state;
initial reactivity of coke in non-catalytic state:
wherein P is g And M g The pressure and the relative molecular mass of the reaction gas g are respectively, and the reaction gas comprises any one of the following components: carbon dioxide, water vapor, oxygen or a mixture of known components and concentration ratios, M C R is a universal gas constant, and gamma is a catalytic factor;
in the prediction unit of the present invention,
coke reactivity R at conversion x x ：
R x ＝R 0 ·f(x)＝R N0 ·γ·f(x)
Wherein x is coke conversion, gamma is catalytic factor, R x R is the coke reactivity at conversion x 0 For the initial reactivity of the coke in the catalytic state, f (x) is a structural function,
where ψ is a structural factor related to the coke pore structure,
ψ＝ηN I ψ I +(1-η)N II ψ II 。
4. the universal prediction system for pyrolysis coke reactivity of solid fuels according to claim 3, wherein in the input unit, the industrial analysis data comprises ash content of solid fuels, fixed carbon content of solid fuels and volatile content of solid fuels, the elemental analysis data comprises carbon element, hydrogen element, nitrogen element, sulfur element and oxygen element content, the internal catalytic elements comprise positive catalytic elements and negative catalytic elements, the positive catalytic element content comprises: the negative catalytic element content is silicon element content and aluminum element content.
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